Near-Infrared Photoelectrochemical Conversion via Photoinduced Charge Separation in Supramolecular Complexes of Anionic Phthalocyanines with Li<sup>+</sup>@C<sub>60</sub>
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- Yuki Kawashima
- Department of Material and Life Science, Graduate School of Engineering, Osaka University, and ALCA, Japan Science and Technology Agency (JST), Suita, Osaka 565-0871, Japan
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- Kei Ohkubo
- Department of Material and Life Science, Graduate School of Engineering, Osaka University, and ALCA, Japan Science and Technology Agency (JST), Suita, Osaka 565-0871, Japan
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- Vicente Manuel Blas-Ferrando
- Área de Química Orgánica, Instituto de Bioingeniería, Universidad Miguel Hernández, Edificio Vinalopó, Avda. Universidad s/n, Elche E-03202, Spain
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- Hayato Sakai
- Department of Chemistry, Faculty of Science and Technology, Keio University, Yokohama 223-8522, Japan
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- Enrique Font-Sanchis
- Área de Química Orgánica, Instituto de Bioingeniería, Universidad Miguel Hernández, Edificio Vinalopó, Avda. Universidad s/n, Elche E-03202, Spain
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- Javier Ortíz
- Área de Química Orgánica, Instituto de Bioingeniería, Universidad Miguel Hernández, Edificio Vinalopó, Avda. Universidad s/n, Elche E-03202, Spain
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- Fernando Fernández-Lázaro
- Área de Química Orgánica, Instituto de Bioingeniería, Universidad Miguel Hernández, Edificio Vinalopó, Avda. Universidad s/n, Elche E-03202, Spain
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- Taku Hasobe
- Department of Chemistry, Faculty of Science and Technology, Keio University, Yokohama 223-8522, Japan
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- Ángela Sastre-Santos
- Área de Química Orgánica, Instituto de Bioingeniería, Universidad Miguel Hernández, Edificio Vinalopó, Avda. Universidad s/n, Elche E-03202, Spain
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- Shunichi Fukuzumi
- Department of Material and Life Science, Graduate School of Engineering, Osaka University, and ALCA, Japan Science and Technology Agency (JST), Suita, Osaka 565-0871, Japan
書誌事項
- 公開日
- 2015-02-09
- 資源種別
- journal article
- DOI
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- 10.1021/jp5123163
- 公開者
- American Chemical Society (ACS)
この論文をさがす
説明
Two phthalocyanines possessing carboxylate groups ((TBA)4H2Pc·1 and (TBA)4H2Pc·2) form 1:2 supramolecular complexes with lithium cation-encapsulated C60 (Li(+)@C60) [H2Pc·1(4-)/(Li(+)@C60)2 and H2Pc·2(4-)/(Li(+)@C60)2] in a polar mixed solvent. From the UV-vis spectral changes, the binding constants (K) were estimated as ca. 10(12) M(-2). Upon the photoexcitation of constructed supramolecular complexes, photoinduced electron transfer occurred to form the charge-separated (CS) state. The lifetime of the CS state was determined to be 1.2 ms for H2Pc·2(4-)/(Li(+)@C60)2, which is the longest CS lifetime among the porphyrinoid/fullerene supramolecular complexes. H2Pc·1(4-)/(Li(+)@C60)2 also afforded the long-lived CS state of 1.0 ms. The spin state of the long-lived CS states was determined to be a triplet, as indicated by the EPR signal at g = 4. The reorganization energy (λ) and the electronic coupling term were determined to be λ = 1.70 eV, V = 0.15 cm(-1) from the temperature dependence of the rate constant for the charge recombination of the CS state of H2Pc·1(4-)/(Li(+)@C60)2. The energy of the CS state (0.49 eV) is much smaller than the reorganization energy, indicating that the back-electron-transfer process is located in the Marcus normal region. The small electronic coupling term results from the spin-forbidden back electron transfer due to the triplet CS state. Supramolecular complexes of anionic zinc phthalocyanines with Li(+)@C60 were also prepared and investigated. The ZnPc·4(4-)/Li(+)@C60 supramolecular nanoclusters were assembled on the optically transparent electrode (OTE) of nanostructured SnO2 (OTE/SnO2) to construct the dye-sensitized solar cell. The IPCE (incident photon-to-photocurrent efficiency) values of OTE/SnO2/(ZnPc·4(4-)/Li(+)@C60)n were much higher than the sum of the two IPCE values of the individual systems OTE/SnO2/(Li(+)@C60)n and OTE/SnO2/(ZnPc·4(4-))n, covering the near-infrared region.
収録刊行物
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- The Journal of Physical Chemistry B
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The Journal of Physical Chemistry B 119 (24), 7690-7697, 2015-02-09
American Chemical Society (ACS)
